CN1743390A - Multilayer coatings having color matched adhesion promoters - Google Patents
Multilayer coatings having color matched adhesion promoters Download PDFInfo
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- CN1743390A CN1743390A CNA2005100990750A CN200510099075A CN1743390A CN 1743390 A CN1743390 A CN 1743390A CN A2005100990750 A CNA2005100990750 A CN A2005100990750A CN 200510099075 A CN200510099075 A CN 200510099075A CN 1743390 A CN1743390 A CN 1743390A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
Abstract
The present invention provides coatings comprising a substrate coated with one or more than one colored primer layer comprising one or more than one binder chosen from a resinous or (co)polymeric primer or adhesion promoter, and one or more than one basecoat color layer thereon, wherein the color of each of the basecoat layer and the colored primer layer are the same. Preferred coatings comprise single colored primer and basecoat color layers to make color coatings having a reduced film build, i.e. two layers. Binders for making primer coating layers may comprise weatherable prime r resins or (co)polymers, or may comprise adhesion promoters chosen from modified isotactic polypropylene (MPP), MPP copolymers, chlorinated polyolefin (GPO), and their mixtures with alkyds or acrylics. In addition, t he present invention provides methods for making coatings on substrates such as thermoplastic polyolefin (TPO), polyolefin containing or metal substrates . Accordingly, the present invention provides color coatings that exhibit improved hiding of dark color or black substrates, such as automotive plasti cs like TPO, made from simplified coating methods.
Description
Technical field
The present invention relates to two-layer or multiwalled water-based or solvent-based coating, wherein the color of the color of prime coat or tackifier layer and undercoat coating or coloured coating is complementary, and also relates to the preparation method of this coating.More particularly, the present invention relates to be used for plastic bottom material, as TPO (TPO), automotive coatings, wherein the color of tackifier layer and undercoat coating is complementary.
Background technology
(for example automotive industry) ground needs two layers of coatings at least in coatings industry, to obtain required color, coating adhesion and weather resistance.With the color is example, and the plastic bottom material of automobile is black or Dark grey especially for the TPO ground of bumper and some internal parts.On these plastic bottom materials, be coated with the priming paint of black or Dark grey in addition.On the metal substrate of automobile, be coated with light grey too to Dark grey or soil Red (muddy red) or brown to dun priming paint.The color of tackifier, priming paint or substrate layer can see through undercoat (base coat) or coloured coating displays as a result, thereby makes setting coat produce undesirable color deviation.Therefore, must on tackifier, priming paint or substrate layer, be coated with a large amount of undercoat or coloured coating, with the undercoat or the coloured coating film of formation thick relatively (for example 25.4-50.8 micron thickness), thereby abundant " covering " or " covering " do not have the ground and/or the arbitrary primer of required color.
Since the cost of pigment, undercoat or the normally the most expensive coating of coloured coating in the middle of industrial ground japanning.Any heavy demand to undercoat or coloured coating all can be raised the auto parts decoration, and for example automobile is decorateed, the painted cost.People need reduce the total cost to metal or the painted coating of plastic bottom material.
Up to the present, except some were used for the epoxy coating of upholster, industrial coating needed at least one deck priming paint or tackifier layer that coating adhesion and weather resistance are provided.Therefore, the coating apparatus that is used for automobile plastic and metal substrate of present nearly all installation is all by comprising that following method makes it to be suitable for forming coating: be coated with tackifier (the similar priming paint of the effect of these tackifier) or priming paint on the ground; Coating one deck or two base coats or coloured coating; Dry a moment; And then be coated with required any finish paint or varnish coating.Yet the covering power of the undercoat that undercoat or coloured coating, particularly color are more shallow or more bright-coloured is not enough to hide the dead color or the dark brown of tackifier/priming paint usually.Therefore, making required coloured coating means will be coated with which floor such layer, the expense that this can cost a lot of money again on the first layer undercoat or coloured coating.People need provide a kind of effective covering effect with the coloured coating method, and hiding does not need coating spreader coating multiple undercoat or coloured coating.
People have done very big effort and have solved the problem that effective covering hides priming paint, and these effort comprise priming paint is become and undercoat color same type or the color coordinated mutually, for example in priming paint, add on a small quantity with undercoat in used identical pigment.Yet priming paint contains and is useful on dark brown filler and the mineral dye that improves its surfacing and grinability up to now, and also the ratio with low relatively pigment/filler and tackiness agent contains limited amount tinting material, in order to guarantee binding property.Therefore, even color is become " coordination " afterwards, undercoat remains dark brown, and this has caused the covering problem, especially for white or yellow and so on light color or red and orange and so on bright color.
In EP communique 0148718A2 number, Panush discloses Tinted clear coatings application system, and it comprises one deck undercoat and at least one aspect enamelled coating and optional prime coat at least, and wherein finish paint can be identical with the color of pigment in the undercoat with pigment in the priming paint.Yet the ratio of pigment and tackiness agent is less than this ratio in the undercoat in finish paint and priming paint.As a result, different pigment ratio being arranged in each Tinted clear coatings, often is that different pigment compositions is arranged, and undercoat and priming paint have material impact to the attractive in appearance of final color, and undercoat provides the color of " being less than the covering effect ".Therefore, when color is estimated, each layer undercoat, priming paint and varnish coating painted seemingly independent; Each layer provides concrete separately aesthetic properties and opacifying property; The final color of coating then is the product of their integral body.In addition, any formulator of this system is necessary for each layer coating unique coating is provided, in order to avoid the main overall color of the color deviation in the product coating.Owing to be to allocate painting color by naked eyes or by colorimetry with the trial and error method of high labour intensity, therefore two or three different particular colors being deployed into required color is a costliness and complicated process to obtain required color combination.At last, Panush never tells about or proposes to hide the coloured coating of Dark grey or black ground.
Among the present invention, thickness or " coating thickness " of the undercoat of present inventor's restriction costliness as possible are with the two-layer coating with essential covering effect that provides.In addition, the present inventor also provides weathering resistance industry and the car paint that has required color with monochromatic allotment.In addition, the present inventor also not needing decoration to change under the prerequisite of at present used undercoat prescription, has solved above-mentioned problem.
Summary of the invention
The invention provides the two-layer or multiwalled coating that is used on plastics or the metal substrate, preferred weather resistant coatings.This coating comprises the ground that scribbles following coating: one or more layers colored primer layer, described colored primer layer is made by a kind of composition, and said composition contains one or more pigment and one or more are selected from the tackiness agent of resin or (being total to) polymkeric substance priming paint or tackifier; With one or more layers undercoat color layer that is coated on the colored primer layer, this undercoat color layer is made by a kind of composition, and said composition contains one or more pigment and one or more (being total to) polymkeric substance or resin.Described undercoat has identical color with the colored primer layer, thereby has improved covering effect, and has reduced the consumption of undercoat under not needing the situation that each layer in any varnish coating of prime coat, undercoat and coating mixed colours separately.In the present invention, term " identical " color is meant when using bore hole to observe, seem any color identical with the color of comparing, perhaps use any means (for example with spectrophotometer or RGB pick up camera) to record and compare colour-change (Δ E), preferably 2.0 or littler random color 2.2 or littler with color standard.
Described coating also can comprise varnish coating on undercoat.This coating preferably includes a colored primer layer and a undercoat color layer, promptly one has two coatings.Under the tackifier situation, described colored primer layer can preferably not contain any (being total to) polymkeric substance or resin that exists in bottom coating composition, and the tackiness agent in the prime coat mainly is made up of one or more tackifier.
In order to improve being generally the ground of Dark grey or black, as TPO (TPO) or contain the covering effect of polyolefinic plastic bottom material, the pigment in one or more colored primers or bonding agent composition with binder wt than (P/B) (with P/B
AExpression) can be equal to or greater than P/B in one or more undercoat colored composition (with P/B
BExpression).Yet, P/B
AAnd P/B
BRatio usually from 0.75 or higher (preferred 0.99 or higher, or 1.0 or higher) to 5.0 (or 2.5).
The composition that is used to prepare prime coat among the present invention contains highly durable tackifier or bottom paint resin or (being total to) polymkeric substance.In order to improve to containing the sticking power of polyolefinic ground or TPO ground, the composition that is used to prepare prime coat preferably contain be selected from chlorinatedpolyolefins (CPO), modification isotactic polyprophlene (MPP), MPP multipolymer, MPP adducts, MPP multipolymer adducts and composition thereof one or more tackifier as tackiness agent.These tackifier more preferably are selected from multipolymer adducts of MPP alkyd resin mixture, MPP multipolymer alkyd resin mixture, chlorinatedpolyolefins alkyd resin mixture, chlorinatedpolyolefins acrylic polymers mixture, MPP acrylic polymers mixture and weathering resistance chlorinatedpolyolefins, MPP or MPP and acrylic polymers, Synolac, carbamate or polyester and composition thereof, to make the weathering resistance prime coat.
In addition, the present invention also provides a kind of method of making coating that goes up at ground (for example metal substrate, TPO ground or contain polyolefinic ground).This method is included on the ground one or more colored primers of coating or bonding agent composition to form one or more layers wet prime coat, said composition contains one or more pigment and one or more tackiness agents, and described tackiness agent is selected from the priming paint or the tackifier of resin or (being total to) polymkeric substance; Carry out drying, form the colored primer layer; Be coated with one or more layers pigmented basecoat composition on the prime coat on the ground, said composition contains one or more (being total to) polymkeric substance or resin glue and one or more pigment; Be cured the back and form undercoat coating and solidified coloured coating; Wherein the color of undercoat color layer is identical with the color of colored primer layer.Before this method also can be included in and solidify on the coating of tint lating the wet pressing wetland be coated with one or more layers wet varnish coating composition, solidify then.The present invention preferably provides weather resistant coatings.
The method that is used to form the coating with good covering performance preferably includes: each priming paint or bonding agent composition and pigmented basecoat composition single coating on ground, are made and have the coloured coating that reduces coating thickness.Therefore, when using tackifier, in the middle of the present invention is used for making one or more compositions of each colored primer of coloured coating and undercoat color layer, P/B
A/ P/B
BRatio can be 0.75 or higher.When using priming paint tackiness agent or tackifier, this P/B
A/ P/B
BThan being preferably 1.0 or higher, promptly one or more are used to form P/B value in the composition of colored primer layer and should be equal to or greater than P/B value in one or more compositions that are used to form the undercoat color layer.More preferably, used painted bonding agent composition does not contain any one (being total to) polymkeric substance or resin used in the undercoat in the inventive method, promptly this painted bonding agent composition contains pigment and any optional component, additive and filler, and one or more tackiness agents of mainly being made up of tackifier resin or (being total to) polymeric viscosifiers.
Embodiment
The invention provides a kind of coating, this coating comprises at least one prime coat and at least one undercoat, and wherein the composition of priming paint forms the prime coat identical with the undercoat color.Partly hide black or dark-coloured ground with prime coat, compare, produce color outward appearance better covering effect of ground and improvement with the coating of using dark brown priming paint to make.The present invention uses less undercoat, thus the molding color method that makes automotive coatings and nearest exploitation be used to make plastic components compare, more competitive on price.For example, on the coating that forms by individual layer priming paint or tackifier coating, be coated with the individual layer undercoat, just can reach fabulous covering effect, the undercoat film thickness that obtains like this is the 10-24 micron, preferred 13-21 micron, and primer film thickness is the 5-12 micron, more preferably 7-11 micron.This coating also can comprise protection finish paint or the varnish coating that is coated on the undercoat, thereby forms the film of 32-51 micron thickness.In addition, the present invention also can provide the single coating finish paint that mainly is made of prime coat and undercoat, and prime coat and undercoat contain weathering resistance (be total to) polymkeric substance or resin and need not any finish paint, thereby remove the expense of protecting varnish coating or finish paint from.
Another advantage of the present invention comprises reducing sprays paint, thus with compare with the made coating of common method, reduced waste when making the filming of equal in quality.In addition, compare, because the coating of single track undercoat needs less spray booth, so the inventive method can reach good covering effect with less maintenance cost with the coating of two pass undercoat.The inventive method can be used for water-based (aqueous) coating composition or solvent based coating composition, powder coating and composition thereof.
All comprise the term that the selection of terms ground expression of parenthesis part contains the term of parenthesis part and do not contain this parenthesis part.For example, represent methylidene vinylformic acid and vinylformic acid can be distinguished in term " (methyl) vinylformic acid ".
All scopes of being quoted among the application are to comprise the scope of first and last and can make up.For example, if component concentration be 4 weight % or more than, 10 weight % or more than, be up to 25 weight %, then this component concentration can be 4-10 weight %, 4-25 weight % or 10-25 weight %.
Unless indicate in addition, the method among all embodiment is all carried out under standard temperature and standard pressure (STP) condition.
Unless indicate in addition the P/B value by calculating each paint base composition and bottom coating composition or calculate P/B by the P/B value of calculating each priming paint rete and undercoat film coating
A/ P/B
BThe ratio.Always coating is compared with coating, composition compares with composition.When using multiple paint base composition, P/B
ARepresent the mean value of all paint base compositions; When using multiple bottom coating composition, also calculate their mean value.Equally, in order to calculate the P/B of multilayer undercoat or prime coat
B, use every layer of all P/B
BMean value.
In this application, term " vinylformic acid " comprises vinylformic acid and methacrylic acid simultaneously, and term " acrylate " comprises acrylate and methacrylic ester simultaneously.
In this application, term " tackifier " is meant (being total to) polymkeric substance or the resin that is used to be coated with non-metal substrate, and term " priming paint " refers to be used to be coated on composition or (being total to) polymkeric substance or resin on the metal substrate.
In this application, term " undercoat ", " coloured coating " refer to identical composition with " single coating ", just do not have varnish coating or top coat layer usually on the single coating.
In this application, " color " of term layer or coating refers to drying, solidifies the color of coating afterwards, and " color " of coating composition refers to the color of composition self.
In this application, term " (being total to) polymkeric substance " refers to one or more polymkeric substance, one or more multipolymers or its mixture.
In this application, term " multipolymer " comprises multipolymer, terpolymer and the polymkeric substance that forms with different monomers or resin polymerization more than three kinds, and in the graft copolymer any.
In this application, term " film thickness " refers to along the cross section of coated membrane 1 cm long, the average film thickness of measuring by microscopic examination at least three points.
Unless otherwise indicated, in this application, term " toxilic acid " comprises toxilic acid or maleic anhydride.
In this application, term " Mn " expression is by the number-average molecular weight of gel permeation chromatography (GPC) mensuration.
In this application, term " MPP or MPP multipolymer adducts " comprises one or more polymkeric substance, resin or reactant (for example Synolac or acrylic polymers or contain one or more reactant of one or more hydroxyls, carboxyl, epoxy-functional, for example glycol or alcohol acid) and the isotaxy MPP of one or more modifications with one or more carboxyls, acid anhydride, hydroxyl or epoxy epoxy-functional or the reaction product of MPP multipolymer." adducts " also comprises one or more polymkeric substance that contain the residual olefin functionality or the reaction product of resin and one or more isotaxys MPP or MPP multipolymer.
Unless indicate in addition, in this application, phrase " each hundred parts " resin or " phr " are illustrated in each hundred weight part gross weight of resin contained in the composition, reactant monomer and polymkeric substance (comprising cross-linked resin and solidifying agent), the weight part that a kind of component is shared.
In this application, term " pigment " comprises pigment, tinting material and dyestuff.
In this application, term " polymer " " comprise polymkeric substance, multipolymer and terpolymer, and segmented copolymer and ternary block polymer.
In this application, phrase " plastic bottom material " refers to TPO, and ground contains the resin of the 50 weight % that have an appointment at least, this resin can be alfon or wherein propylene monomer content be at least the multipolymer of 60 weight %.
In this application, term " molded article " comprises stampings, casting article (for example by dehydration from suspension or remove the brake-shoe that desolvates and make) and the multilayer film and the laminated product of the forged article, sheet and so on of plastic molded product and metal moulded parts, disc spring and so on.
In this application, term " finish paint " and " coloured coating " can exchange.
In this application, phrase " solid amount " refers to after removing the volatile component, remaining organic and inoganic solids shared weight percentage in composition total weight.
In this application, term " TPO " refers to contain the polypropylene of the compound of useful modified rubber.
In this application, term " wt% " expression weight %.
In this application, gel permeation chromatography or the measured polymkeric substance molecular-weight average of density gradient sedimentation method are used in subject " weight-average molecular weight " expression.
Be used to make the composition of coating of the present invention and will can be mixed with multiple coating and liquid film-forming composition according to the composition that the inventive method is used.These compositions comprise solvent-borne type or the waterborne compositions as priming paint or tackifier, as the solvent-borne type or the water-based type composition of undercoat, crosslinked undercoat, coloured coating, finish paint and varnish coating, and be used to form any powder coating in prime coat, undercoat, single coating, top coat layer and the varnish coating.Finish paint and varnish coating contain weathering resistance resin or (being total to) polymkeric substance usually, and/or the amount that contains pigment or contained pigment can access transparent or semitransparent film, or do not contain pigment.
As the priming paint among the present invention or the composition of tackifier, comprise in following each component one or more: (i) be selected from the tackiness agent of tackifier or bottom paint resin or (being total to) polymkeric substance, (ii) tinting material or pigment.Said composition can be used as undercoat, single coating or the coloured coating among the present invention, finish paint and varnish coating, and it comprises in each component of resin or (being total to) polymkeric substance and tinting material or pigment one or more.
Be used for one or more (being total to) polymkeric substance of undercoat, coloured coating, finish paint and/or varnish coating or resin and comprise in multiple thermoplasticity and thermoset (being total to) polymkeric substance or the resin any.
In waterborne compositions, useful (being total to) polymkeric substance or resin can comprise one or more polyolefine, acrylic polymers, acrylic acid modified alkyd resin, polyester, polymeric amide, urethane, blocked polyisocyanates and composition thereof, grafts and multipolymer, preferred weathering resistance (being total to) polymkeric substance or resin.Water dispersion also can comprise anionic property, cationic or nonionic water dispersion, and this water dispersion can use dispersion agent, emulsifying agent or tensio-active agent to form, and also can form without these components.
(being total to) polymkeric substance or resin used in the organic solvent type composition of the present invention comprise Synolac, urethane, polyester, acrylic polymers, acrylic acid modified alkyd resin and composition thereof and combination.Preferred solvent-borne type (being total to) polymkeric substance or resin can comprise Synolac, urethane, polyester, acrylic polymers and the acrylic acid modified alkyd resin of one or more larger molecular weights, and they have the carboxy lower value of low hydroxyl value and the 1-10 of 1-10 separately.Preferred polymkeric substance is soluble in organic solvent, forms film and coating with excellent mechanical properties.Solvent based coating more preferably comprises weathering resistance (being total to) polymkeric substance or resin or its mixture.
Be used for " weathering resistance " (being total to) polymkeric substance of single coating or resin or its blend and may be defined as any one or multiple (being total to) polymkeric substance or resin or its blend after coating or the film of solidifying to form that meets the following conditions: wherein residual epoxy group(ing), oxygen activity functional group (for example alkyd or acetoxyl group), the content of ultraviolet (UV)/visible radiation active function groups (for example allyl group or vinyl or vinylformic acid) or water active function groups (for example not end capped isocyanic ester) is lower than 0.5 weight % (is benchmark in the weight that (is total to) polymkeric substance or resin in film or the coating).These residual epoxy group(ing), oxygen activity functional group, ultraviolet (UV)/visible radiation active function groups or the content of water active function groups in weather resistant coatings or film can be less than 0.2 weight %, or less than 0.05 weight %, or less than 0.02 weight %.
Weathering resistance (being total to) polymkeric substance or the resin that are applicable to the aqueous basecoat layer composition can be selected from bi-component polyester (for example carboxyl and hydroxyl-functional component), two component polyurethane (for example isocyanic ester and hydroxyl-functional component), polyester-trimeric cyanamide, acrylic acid or the like-trimeric cyanamide, thermoplastic acrylic polymer, the single component polyester, be mixed with the acrylic polymers or the polyurethane polyol of end capped isocyanate crosslinking, alkyd modified acrylic polymers, and any one or multiple (being total to) polymkeric substance or the resin that can be used in varnish coating and finish paint.
Be applicable to that weathering resistance (being total to) polymkeric substance of solvent based coating or resin comprise one or more two component polyurethanes or polyester, vinylformic acid-trimeric cyanamide, polyester-trimeric cyanamide, single component polyester, the acrylic polymers that is mixed with the blocked isocyanate linking agent or polyurethane polyol, alkyd modified acrylic polymers and can be used in varnish coating and any one or multiple (being total to) polymkeric substance or resin of finish paint.
The preferred composition that forms varnish coating and finish paint can comprise be used for insect protected and sun-proof curable epoxy official can material, said composition also contains usually and is useful on one or more urethane that flexible and weathering resistance are provided, polyester, acrylic polymers and composition thereof or makes up.
The multipolymer in undercoat, coloured coating, single coating, finish paint or the varnish coating composition or the content of resin can be from 20 weight % or above (gross weight in composition is a benchmark), from 30 weight % or more than, to 70 weight % or following, or 50 weight % or following, or 40 weight % or following.
In undercoat powder coating of the present invention, suitable (being total to) polymkeric substance or resin can comprise, for example weathering resistance polyester epoxy hybridization thermosetting resin, the vibrin that is mixed with triglycidyl isocyanurate (TGIC), beta-hydroxy alkylamide or poly carboxylic acid (for example laurostearic acid) or anhydride curing agents, vinylformic acid or urethane ester polymer or hybridization thing and composition thereof.The content that (is total to) polymkeric substance and resin in the undercoat powder coating can be 40-95 weight % (is benchmark in the composition total weight).
The solidifying agent that is used for any kind coating composition can comprise that those are suitable at the solidifying agent that is lower than thermofixation under 150 ℃ the substrate surface temperature, preferably, this solidifying agent can or be lower than under 121 ℃ the frosting temperature and solidify, and can solidify being lower than under 105 ℃ the wood surface temperature.They comprise end-blocking catalyzer or solidifying agent, arbitrarily bicomponent system second kind of component (for example trimeric cyanamide or isocyanic ester), imidazoles-amine and be used to contain the epoxy-amine adducts (powder coating that for example is used for timber) of Resins, epoxy.
In the present invention, the priming paint of color-match or bonding agent composition unexpectedly have acceptable bond properties, even when adding pigment, when making the color of the made coating of these compositions be complementary with the color that is coated on the undercoat on priming paint or the prime coat, said composition still has this acceptable bond properties.For fear of the dilution tackifier, preferred bonding agent composition does not contain undercoat (being total to) polymkeric substance or resin.
Be applicable to that tackifier (being total to) polymer binder that contains polyolefinic ground or TPO ground comprises chlorinatedpolyolefins (CPO), low-molecular-weight isotaxy modified polypropene (MPP), MPP adducts, poly-(propylene-alpha-olefin) multipolymer (MPP multipolymer) of low-molecular-weight isotaxy modification, MPP multipolymer adducts, MPP alkyd resin mixture, chlorinatedpolyolefins alkyd resin mixture and composition thereof and combination.
The tackifier tackiness agent preferably includes chlorinatedpolyolefins, MPP, MPP multipolymer or is mixed with the MPP adducts of weathering resistance membrane-forming agent (for example Synolac, acrylic polymers, Synolac, carbamate or polyester).The mixture or the adducts of special preferred alcohols acid resin and chlorinatedpolyolefins, MPP, MPP multipolymer or MPP adducts, this is because therefore they can be suitable for the wet coating of wet pressing at air drying very much.Described chlorinatedpolyolefins-Synolac, MPP-Synolac or MPP multipolymer alkyd resin mixture should contain enough chlorinatedpolyolefinss, make it to be bonded on the ground, therefore the content of chlorinatedpolyolefins account for the resin solid gross weight 5 weight % or more than, 8 weight % or more than, preferred 10 weight % or, be up to 40 weight %, preferably be up to 25 weight %.
Suitable chlorinatedpolyolefins can be the amorphous or crystallization poly-alpha-olefin of chlorating, randomly contains carboxyl.Chlorinatedpolyolefins can comprise propylene dichloride homopolymer or any propylene-alpha-olefin copolymers, and the monomer content of propylene is at least about 60 weight % in this multipolymer.In order to obtain suitable film forming characteristics, the weight-average molecular weight of carboxylic poly-alpha-olefin is 4000-150000, preferred 5000-80000, more preferably 25000-50000; The softening temperature of described carboxylic poly-alpha-olefin is 75-115 ℃, and cl content is 10-35 weight % (is benchmark in polyolefinic weight).
Can carry out further modification to not carboxylic chlorinatedpolyolefins, for example grafting imide or contain the carboxylic acid group or with acid anhydride's monomer (for example maleic anhydride) modification.If carry out further modification with imide, add the 0.001-10 weight % that imido amount is about polyolefine weight.If carry out further modification with the monomer that contains carboxylic acid group or acid anhydride, add the 0.001-10 weight % that monomeric amount is about polyolefine weight.
The example of chlorinatedpolyolefins can comprise the multipolymer of chlorinatedpolyethylene or Chlorinated Polypropylene III or they and one or more alpha-olefins.Can use acrylic resin that chlorinatedpolyolefins is carried out grafting, make it can be more compatible, make also that itself and ABS's and so on contain more consistency of acrylic acid or the like ground with undercoat that contains acrylic acid or the like or coloured coating.
The solidifying agent that is used for acid or anhydride-functional chlorinatedpolyolefins or is used for the acrylic polymers graft chlorinated polyolefin can comprise trimeric cyanamide and isocyanic ester, and the hydroxy-functional acrylic resinoid.Hardener dose should make the solidifying agent and the ratio of the stoichiometry of chlorinatedpolyolefins can be 0.6: 1.0-1.3: 1.0.These solidifying agent can be used for thermally sensitive plastic bottom material.
The water dispersible chlorinatedpolyolefins that is used for water-borne coatings can contain any polymkeric substance that meets following condition: the weight in the reactant that is used to prepare polymkeric substance is benchmark, and polymkeric substance contains one or more unsaturated acid or the unsaturated acid anhydride of 0-10 weight %.The preferred ammoniacal liquor that uses carries out part neutralization or neutralization fully to the water dispersible chlorinatedpolyolefins, or more preferably uses dimethyl ethanol (DMEA) amine to make it be partially soluble in water.
MPP or MPP multipolymer can be polypropylene or poly-(propylene alpha-olefin) multipolymer of any modification, described modification can following mode be carried out: for example in the presence of ozone, hydrogen peroxide, perborate or periodate and so on oxygenant, carry out modification by oxidation; Perhaps in the presence of initiator, carry out modification with one or more unsaturated reactant reactions, described unsaturated reactant contains the combination (for example toxilic acid or acid anhydrides) of one or more carboxyls, acid anhydride base, hydroxyl or epoxy group(ing) or these groups.The multipolymer of described one or more low-molecular-weight isotaxy MPP or MPP preferably has one or two end thiazolinyl.Preferably, can carry out modification, generate one or two end anhydride group, end carboxyl, terminal hydroxy group or end epoxy group(ing) by one or two end thiazolinyl of described MPP of reaction pair or MPP multipolymer.Preferred terminal-modified isotaxy MPP or MPP multipolymer a variety of prescriptions with use in all shown consistent dispersiveness and bond properties.And, terminal-modified MPP or MPP multipolymer can with acrylic polymers that contains carboxyl or hydroxyl or resin reaction, generate MPP or MPP multipolymer-acrylic polymers adducts, this adducts make the acrylic acid or the like undercoat and contain polyolefinic ground or the TPO ground between consistency be improved.
Lower molecular weight isotactic polyprophlene (PP) or PP multipolymer that correctability generates MPP or MPP multipolymer can be any (be total to) polymkeric substance that meets the following conditions: the number-average molecular weight (Mn) that this (being total to) polymkeric substance records by gel permeation chromatography be from 500 or more than, for example from 800 or more than, from 1000 or more than.In addition, the number-average molecular weight of suitable PP or PP multipolymer should be up to 10000, for example is up to 7000, or is up to 4000, or is up to 2500.The melt viscosity of these (being total to) polymkeric substance can be 20-300cP under 149 ℃.
Gross weight in contained monomeric unit in the polymkeric substance is a benchmark, and the PPs that is fit to modification contains " degree of isotacticity " or the isotactic unit of 90 weight % or following and 40 weight % or above (for example 60 weight % or more than).Suitable PP (being total to) polymkeric substance should contain 9 weight % or more than, for example 40 weight % or more than and 90 weight % or following, or 60 weight % or following, or 40 weight % or following this isotactic propylene unit.High isotactic (degree of isotacticity≤60 weight %) PP has definite melting point and narrow surprising molecular weight distribution.This isotactic PP and PP multipolymer have narrow molecular weight distribution, and its polymolecularity is 1.5-3.0 (for example 1.5-2.5), and resulting coating or film have controlled and expected film forming and adhesion characteristics therefore (for example (to be total to) fusing point of polymkeric substance) under preset temperature.
Suitable isotaxy PP multipolymer that can modification can be the random copolymers that meets the following conditions: the weight in the reactant that is used for preparing multipolymer is benchmark, the content of propylene is no less than 10 weight % (for example being no less than 40 weight %) in this multipolymer, also contains high alpha-olefin (promptly containing 3-12 carbon atom); Or be the segmented copolymer of the polymkeric substance of polypropylene and high alpha-olefin.The example of high alpha-olefin comprises 1-butylene, 1-amylene, 1-octene and preferred 1-hexene.Therefore, available isotactic modified propylene/hexene, isotactic propene/but-1-ene and isotactic propene/but-1-ene/hexene copolymer illustrate the isotaxy PP multipolymer that is used for modification, and wherein every kind of multipolymer can contain one or two end thiazolinyl.The mixture and the propylene of two or more these high alpha-olefins can be carried out copolymerization.
Carboxyl and acid anhydride base modification group should come from the reaction of MPP or MPP multipolymer and toxilic acid or maleic anhydride group, also can come from fumaric acid, methylene-succinic acid, citraconic acid, allyl group succsinic acid, methylfumaric acid and equisetic acid and their acid anhydrides.Weight in carboxylic acid or anhydride modified multipolymer is benchmark, α, the consumption of β-unsaturated dicarboxylic acid or its acid anhydrides can be from 1 weight % or more than, 2 weight % or more than, 4 weight % or more than, to 20 weight % or following, or 10 weight % or following, or 7 weight % or following, more preferably 4-7 weight %.Also can pass through unsaturated group and the isotactic PP or the PP copolymer reaction of unsaturated carboxylic acid, acid anhydrides, alcohol, glycol, polyol or alcohol acid, prepare isotaxy MPP and MPP multipolymer that other is fit to.Preferred epoxy-terminated isotaxy MPP and MPP multipolymer can be available from Texas Sugarland, the Baker Petrolite polymkeric substance department of Baker Hughes company.
1-10 be can contain in suitable isotaxy MPP or the MPP multipolymer per molecule, preferred 1-5, more preferably carboxyl, end acid anhydride base, end epoxy group(ing) or terminal hydroxy group held for 1 or 2.Can select to contain the isotaxy MPP and the MPP multipolymer of 1-5 carboxyl, acid anhydride base, hydroxyl or epoxy group(ing), because they have good solubleness in dimethylbenzene, toluene and other organic solvent; Also can select to contain the isotaxy MPP and the MPP multipolymer of 2-10 carboxyl, acid anhydride, hydroxyl or epoxy group(ing), should be them and have water dispersible.
Because the fusing point of isotaxy MPP or MPP multipolymer is 80 ℃ or above (for example 105 ℃ or more than) and is 145 ℃ or following, these polymkeric substance can make coating of the present invention, priming paint and film-forming composition to TPO or contain polyolefinic plastic bottom material and have and better soak and osmotic effect, thereby have improved bonding to these grounds of under the temperature that is lower than ground heat damage coating.The fusing point of the suitable isotaxy MPP of degree of isotacticity≤60 weight % (weight in multipolymer before the modification is benchmark) will be lower than the fusing point of the MPP homopolymer with identical Mn.Therefore, isotaxy MPP multipolymer, particularly those Mn be 4000 or following MPP multipolymer should be used for the low-temperature curing purposes, for example under 160-250 °F (71-121 ℃) on the automotive interior plastics solidified coating, for example those are at 160-200 (71-93.3 ℃) following solidified coating.
In another embodiment, paint base composition also can contain chlorinatedpolyolefins except isotaxy MPP or MPP multipolymer or adducts (preferably can be used as isotaxy MPP or the MPP multipolymer or the adducts of the epoxy-functional of chlorinatedpolyolefins stablizer).These compositions also can contain Synolac or Synolac adducts.Reduce the content of chlorinatedpolyolefins in the said composition, thereby also reduced the content of chlorine.Except isotaxy MPP or MPP multipolymer, the solvent bottom paint composition can contain the highest 60phr, the chlorinatedpolyolefins of preferred 0-40phr.And except isotaxy MPP or MPP multipolymer, waterborne compositions can contain the highest 90phr, the chlorinatedpolyolefins of preferred 0-60phr.
For the wearing quality that increases film, layer or coating and the consistency between them, some undercoat or the finish paint in the paint base composition in primer film, layer or the coating and other coating can be complementary.For example, at least a portion in (being total to) polymkeric substance at least a in undercoat, coloured coating, single coating, finish paint and/or the varnish coating or the resin can be compatible with polymkeric substance or resin, tackifier or the priming paint of top painting bottom coating, coloured coating, single coating, finish paint and/or varnish coating.
The priming paint binder composition of the suitable coupling of Shi Yonging and basecoat polymers or resin combination comprise together: polyester-trimeric cyanamide or acrylic acid or the like-trimeric cyanamide, together use with single component polyester-trimeric cyanamide or acrylic acid or the like trimeric cyanamide; Acrylic acid or the like-isocyanic ester or polyester-isocyanic ester use with bi-component polyester (carboxyl and hydroxy component) or two pack type acrylic-isocyanic ester; Polyurethane paint in the solution system uses with urethane undercoat arbitrarily.Acrylic polymers or resin can comprise acrylated Synolac, thermoplastic acrylic polymer and hydroxy-functional acrylic base polymer.Polyester can preferably include the hydroxyl-functional polyester, for example hexanodioic acid trishydroxymethyl propyl ester.Except the polyurethane paint that is used for solvent-based system, any tackiness agent above all can be used for water-based or solvent-borne type liquid system.
The bonding agent composition and the bottom coating composition of appropriate coupling can comprise acrylic polymers-polyolefin blend compound or contain the grafted undercoat that this undercoat is coated on the prime coat that contains modified polyolefin.
Under the tackifier situation, for fear of the dilution tackifier, the composition that is used for making prime coat does not preferably contain basecoat polymers or resin.These compositions for example, contain the paint base composition of carboxylated isotactic polyprophlene or Chlorinated Polypropylene III, should not comprise the polypropylene in the undercoat that contains polypropylene-acrylic acid or the like, although can form compatible coating or film mutually.
Gross weight in composition is a benchmark, the content of tackiness agent (being total to) polymkeric substance or resin is up to 50 weight % in water-based or solvent bottom paint or bonding agent composition, or be up to 40 weight %, preferably be up to 25 weight %, and this content should be not less than 5 weight % or more than, preferably be not less than 15 weight % or more than.In the solid amount is benchmark, can contain 5 weight % or above or 7 weight % or above, 10 weight % or above one or more priming paint or tackifier polymkeric substance or resin.Gross weight in composition is a benchmark, and in powder paint compositions, the content of tackiness agent (being total to) polymkeric substance or resin can be 40-95 weight %.
The pigment or the tinting material that can be used for liquid system comprise any automotive grade (automotive grade) organic or inorganic pigment.In powder systems, can use any pigment.
For example, suitable pigment can comprise titanium dioxide, aluminum paste (aluminum paste), mica, coated mica, phthalocyanine green, phthalocyanine blue is red, phthalocyanine is red, phthalocyanine is bluish-green, phthalocyanine blue, phthalocyanine is turquoise, phthalocyanine is greenish-yellow, phthalocyanine green special yellow (extra yellow), copper phthalocyanine, indanthrene blue, chromoxide green, azophosphine, indanthrene blue, cobalt blue, barba hispanica, dinitro aniline orange (dinitriline orange), the dianisidine orange, the monoazo orange, molybdate orange, imidazoles orange perylene maroon-transparent, red iron oxide, Zh 1, transparent red iron oxide, the glassy yellow ferric oxide, quinacridone is red, quinacridone is purplish red, quinacridone golds, quinacridone is deep red red, quinacridone violet, toluidine red perylene is red, anthraquinone is red, cadmium red, BON is red, monoazo is red, (diketo-pyrrolopyrrole) is red for diketopyrrolopyrrolecocrystals, Crow Mu Futa (chromophtal) is red, carbazole violet, titanium nickel yellow, titanium chrome leather Huang, chrome yellow, the flavanthrone Huang, anthrapyrimidine yellow, the isoindolinone Huang, metal chelation azo (copper, nickel etc.), carbon black, graphitized carbon black and thioindigoid maroons.
Painted generally including to arbitrary primer or tackifier, undercoat or coloured coating composition used one or more pigment, normally more than three kinds or three kinds, can comprise inorganic and/or pigment dyestuff.Usually, when prime coat and and coloured coating or undercoat when being same color, each composition that is used to make coating contains identical pigment composition, and pigment solids also can be identical with respect to the weight content of adhesive solids, and promptly they have identical P/B ratio.Have suitable binding property and film forming characteristics in order to ensure coating and film-forming composition, the ratio of the total amount of used pigment and tackiness agent (is benchmark (total P/B) in the solid weight) has following provisions: for metal oxide pigment, the used inorganic, metal oxide total amount and the ratio of tackiness agent should be up to 1.63: 1 in composition, coating or the film, and the ratio of the total amount of other all mineral dyes or pigment dyestuff and tackiness agent should be up to 1.31: 1.
Preferably, for some pigment, total P/B of metal oxide can be up to 0.65: 1; Can be up to 0.26: 1 for carbon black, preferably be up to 0.10: 1; Can be up to 0.50: 1 for aluminium or aluminum paste, or the highest 0.26: 1, or the highest 0.13: 1; Can be up to 0.39: 1 for mica or coated mica.Preferably, total P/B of pigment dyestuff can the highest 0.20: 1 and be 0.01: 1 or more than.When using pigment composition, total P/B of two kinds of composite pigments can be up to 3.0: 1 and should be not less than 0.04: 1.Therefore, if use titanium dioxide, cobalt oxide coated mica with the red mixture of perylene, total P/B of this composite pigment should be up to 2.94: 1, and total P/B of two kinds of metal oxides should be up to 1.63: 1 red total P/B of ， Er perylene and be up to 1.31: 1 in the said composition.
In the composition that is used to form the coloured substrate layer of less solid content, the P/B (P/B of colored primer or bonding agent composition
A) can be far longer than the P/B (P/B of pigmented basecoat composition
B).P/B
A/ P/B
BRatio can be up to 5.0, or be up to 3.0, or be up to 2.5.Under the paint base composition situation, P/B
A/ P/B
BRatio be generally 1.0 or more than, and under the bonding agent composition situation, P/B
A/ P/B
BRatio be generally 0.75 or more than.
Suitable liquid composition contains carrier and solvent, also can randomly contain the anti flocculant that is useful on stable color and be used to keep thixotrope, rheology modifier or the dispersion agent of the stable and levelling of coating.
In solvent-based compositions, solvent can contain priming paint or the bonding agent composition (gross weight in composition is a benchmark) of the highest 95 weight %, preferably be up to 80 weight %, more preferably be up to 60 weight %, and the preferred solvent consumption is not less than 40 weight % (in the gross weight of composition), described solvent comprises as aromatic solvent, for example the mixture of dimethylbenzene, toluene, aromatic fraction and aromatic fraction and their mixture; Ester class, for example isobutyl acetate, propylene glycol methyl ether acetate, isobutyl isobutyrate and composition thereof; Ketone with Methyl amyl ketone and so on.
The ratio of used water and other carrier should be identical with the ratio of used solvent in the solvent-based compositions in waterborne compositions.Also can use solubility promoter in the waterborne compositions as N-Methyl pyrrolidone and ethylene glycol monobutyl ether and so on.The total amount that used water or carrier add solubility promoter shared ratio in waterborne compositions, should with time that do not contain solubility promoter institute's water suitable total amount proportion identical.The add-on of solubility promoter should be up to 10 weight %, preferably the highest 5 weight %, and preferable amount is not less than 2 weight %.
Can in composition, add one or more thixotropes, for example in solvent-based compositions, can add polyamide wax dispersion, pyrogenic silica and organophilic clay (for example hectorite trialkyl aryl or montmorillonite trialkyl aryl, or be scattered in silicon-dioxide in the acryloid cement; In waterborne compositions, can add unmodified clay, for example the composition of hectorite or bentonite and ether of cellulose and cellulose ester.Total consumption of thixotropic agent accounts for the 0.01-5 weight % (is benchmark with the solid) of composition total weight, preferred 0.1-3 weight %.
The anti flocculant (for example solution of the polysiloxane of 10 weight % in pimelinketone) that can in the bonding agent composition that contains chlorinatedpolyolefins and MPP, add the highest 3 weight % (gross weight in composition is a benchmark), preferred 0.5-1.5 weight %.
The nonionic surfactant that can in waterborne compositions, add 0.1-1.0 weight % (gross weight in composition is a benchmark), preferred 0.1-0.5 weight %, the example of described nonionic surfactant comprises polyoxyethylated nonylplenyl ether and polyacrylic acid or alkali-soluble polymer dispersion agent.
Can in waterborne compositions, add solvent oil (mineral spirite) as defoamer.
Powder paint compositions can randomly contain: the filler of 0-120phr; 0.1-1.0phr catalyzer (for example thermal initiation of cobalt octoate and so on and light-initiated redox catalyst); 0.1-1.0phr glidant (for example thermoplasticity (methyl) alkyl acrylate copolymer); As doing the 0.1-1.0phr master stream additive (for example metal oxide of pyrogenic silica and so on) that mixes additive; 0.1-1.0phr flow agent (for example silicone resin).
Amount of filler is for example 10-120phr in the powder paint compositions.The zinc that for example, can contain one or more isotaxys MPP or MPP multipolymer or adducts and 25-120phr as the rich zinciferous corrosion resistant powder coating of priming paint.Also can in the undercoat powder coating, mix the zinc of same ratio.Described exemplary primer powder coating can directly be coated on the untreated steel ground, or is coated on TPO or contains on the polyolefinic ground, and then the liquid or the powder basecoat of coating random color coupling, to form corrosion resistant topcoat.In another example, by adding wollastonite, silicate or the pearl filler of 10-120phr, can form veined topcoat.
The component of the powder coating that is useful on all should be for solid-state.Liquid (for example some organic colorants and pigment, and liquid resin) arbitrarily should be absorbed on the solid carrier of silicon-dioxide and so on and be used for powder coating.Preferably, contained resin or (being total to) polymkeric substance should not soften, melt or flow being lower than under 40 ℃ the temperature in the powder paint compositions.
The used arbitrary composition (for example priming paint or undercoat or varnish coating) of the present invention all can prepare by common method, for example, component is added in the mixing vessel with random order, carries out high-speed stirring or high-shear and stir in dissolver.In order to promote dissolving, with component at least 5 ℃, preferred 22 ℃ or more than, mixed and the highest 44 ℃, mix under the preferred the highest 28 ℃ temperature.Powder coating can prepare by the following method, for example component melt is mixed or extrudes, and cools off then, and grind into powder also mixes additive and mixes mutually with doing.
Can use coating coating apparatus (for example electrostatic spraying device and air pressure spraying equipment, for example electrostatic painting rifle or air pressure varnish spray gun or static clock (bell)) arbitrarily commonly used to be coated with coating of the present invention.Can use any electrostatic applications device coated powder coating, also can use any fluidized-bed or Magnetic brush to be coated with.
Can come the coating composition composition with two spray booths (booth) (first priming paint, undercoat then) or the wet coating composition system of three spray booths (priming paint-undercoat-undercoat) wet pressing.In addition, should be to add the one or more tackifier or the priming paint recycle system on the priming paint spray booth at first spray booth.This recycle system makes tackifier or priming paint supply line flow through one " paint kitchen ", and the combination of employed all different colours (for example 10-50 kind) is being controlled in this paint kitchen, different colours can be transported to same coating apparatus (for example varnish spray gun).This recycle system can enough random colors to tackifier or paint base composition and undercoat or coloured coating composition match colors automatically, therefore can save second undercoat paint spray booth.
Can be cured coating composition by dry air, also can be randomly by heating (for example thermofixation in IR bake or convection oven), solidify or the arbitrary combination of these methods is cured through ultraviolet (UV).By using the wet system of wet pressing, be coated with all coatings and only need carry out one-step solidification afterwards.When using the composition of two-pack, must continue to carry out thermofixation, also have cured up to the second all components.Should under the temperature of regulation, toast or thermofixation,, also tackle composition and select to make it under this temperature, to solidify in order to avoid damage the thermo-sensitivity ground.The surface temperature of heating of plastic should be above 121 ℃.Brass can't stand the surface temperature more than 177 ℃.The surface temperature of timber should be above 105 ℃.The example that is used for the coating composition of low-temperature curing comprise Synolac-dry air coating, can be at solidified resin under the action of UV radiation (for example unsaturated polyester or acrylic polymers), two-component composition, contain the single-component composition (for example blocked isocyanate or end-blocking acid) of end-blocking (blocked) catalyzer and contain the composition of solidifying agent, described solidifying agent makes said composition to solidify under said temperature.
Coating, priming paint and bonding agent composition should be coated on the metal, the example of described metal comprises any alloy or the Industrial Metal ground of being made by aluminium (for example Ji Ya window sectional material (profile)), iron, steel (for example crossbeam and dagger), zinc, brass, copper, molybdenum or titanium and any mixture thereof.Powder coating should be coated on timber, glued board, fiberboard and the panel.In addition, said composition also can be coated on the plastic bottom material.The suitable plastic ground can comprise, for example polyolefine, nylon, polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) (ABS) and sheet material formed composite material (SMC) arbitrarily.
Preferably, in the coating plastic bottom material, it is perhaps identical mutually with this ground to be coated in priming paint on the ground or the tackifier tackiness agent at least a comonomer or starting material component.For example, for acrylonitrile-butadiene-styrene (ABS) (ABS) ground, preferred acrylic acid or the like-trimeric cyanamide priming paint, even more preferably acrylic acid or the like-altogether-vinylbenzene-trimeric cyanamide priming paint; Equally, for containing polyolefinic ground, preferably contain polyolefinic tackifier.
Described water-based, solvent-borne type and powder primer or bonding agent composition can directly be coated internal part or external component (for example those contain TPO or polyolefinic parts), the trolley part that contains ABS resin and the industrial part (for example brake component) of automobile and be used for the sheet material formed composite material (for example roofing board, galley equipment and bath apparatus or ski) of any purposes.The automotive interior ground can include, but are not limited to dashboard, switch and knob, internal mode goods and plate (for example door-plate), inside gadget and the air bag of automobile.The automobile external ground can comprise car body, collision bumper, covering and exterior trimming parts, also comprise under the bonnet and car body under ground.In the time of on being used in the automotive interior ground, can contain low-temperature bake (for example 160-250 or 71-121 ℃) composition at coating of the present invention, priming paint and film-forming composition, in order to avoid damage thermally sensitive ground.
Perhaps, coating composition all can be used as moulding compound, film-forming composition and molded article formation composition (for example being used for lamination and decal process) arbitrarily, or being used to make the batch of material that can stablize storage, this batch of material can add in liquid coating and the film-forming composition.
In following embodiment, used part or all of following testing method:
1. test the coating thickness (film builds) of undercoat and priming paint with ASTM method D-1005-51 ((in June, 1979), " detection of organic coating film thickness ").Use Bausch and Lomb Microzoom II microscope to read coating thickness.The calibration in per at ordinary times six months of this microscope once.The unit of coating thickness is mil (1 mil is equivalent to 25.4 microns).
2. use ASTM method D-2197-68 ((in October, 1981), " sticking power of organic coating ") to measure the sticking power (cross-hatching sticking power) of coating to ground.The result is recently to represent (is benchmark with the coating total area) to the sticking power percentage that ground was kept.
3. under 100 °F (38 ℃), measure wet fastness at the indoor ASTM method of Atlas SF850 relative humidity D-2247-02 ((in August, 2002), " wet fastness of coating under 100% relative humidity ").Humidity chamber calibration in per at ordinary times 6 months once.Panel was placed in humidity chamber 96 hours, and measured the sticking power per-cent (is benchmark in the coating total area) that is kept.
4. use the polygonal spectrophotometer of X-Rite MA6811 to measure the color of tackifier/base coat systems, draw the reading of colorimetric, the calibration in per 6 months of this spectrophotometer once.(25 °, 45 ° and 75 °) measure color property on three angles, and the result is compared with the colorimetric computer standard of the contrast base coat systems of preservation.The result represents that with Δ E the unit of color change is compared in Δ E representative with contrast.The reading of≤2 units is commonly referred to be the acceptable color, if but find that a kind of color seems to be complementary with color standard, even this reading is slightly larger than 2 units, also think acceptable.With coating spraying 4 " * 6 " on the thermoplastic olefin base plate of (101.6 millimeters * 152.4 millimeters) (CA186, available from BasellPolyolefins, Lansing, MI.), coat-thickness is the 10-20 micron.
Embodiment-the be coated on coloured coating on the TPO ground
Under envrionment conditions, use Cowles blade and air mixer to carry out moderate stirring, the various components in the laboratory containers are mixed, thereby prepare tackifier resins intermediate as shown in table 1.
Shown in the following tabulation, in embodiment 1,2,3 and 4, under breadboard envrionment conditions (～25 ℃), use the air mixer to prepare the listed painted tackifier preparation of following table.When mixing under the low shearing of Cowles blade mixer of using the laboratory size and disperseing, to wherein adding pigment dispersion, aluminium and micaceous pigment composition at 500-700 rev/min.After component added, various painted tackifier stirred 30-45 minute.Use the compressed-air actuated Binks 95 type varnish spray gun of supply various colored tackifier to be sprayed on the plate of being made by the TPO ground of Dark grey then, this board size is 4 " * 12 " (101.6 millimeters * 152.4 millimeters).Air atomizing is set at 60psi, and the thickness setting of target prime coat dry film is the 10-20 micron.Use then and supply with (polyester/trimeric cyanamide) automobile undercoat of compressed-air actuated Bink 95 type varnish spray gun in the plate upper surface coating last layer single component of each painted tackifier layer processing, the color of this undercoat and the color of painted tackifier are identical, to hide ground fully.Air atomizing is set at 60psi.Under envrionment conditions, dodge and do (flash) after 5 minutes, use and supply with compressed-air actuated Bink 95 type varnish spray gun are coated with one deck single component again on pigmented basecoat (acrylic acid or the like trimeric cyanamide) automobile varnish coating.Air atomizing is set at 60psi, and target varnish coating build is the 37.5-44.5 micron.Place in the Blue M Electric Laboratory Oven being coated with the plate that obtains like this, solidified 30 minutes down, then it is tested at 250 °F (121 ℃).
The weight percent of term " NVM " expression non-volatile substance.
Table 1: tackifier resins intermediate:
| Component | Weight percent |
| Styrene alkyd resin (50 weight % solids in the dimethylbenzene) | 11.91 |
| Chlorinatedpolyolefins intermediate (in the mixture of 54.3 weight % dimethylbenzene, 25.7 weight % hexanaphthenes and 5 weight % pimelinketone, 15 weight % solids) | 14.23 |
| Dimethylbenzene | 31.63 |
| Toluene | 9.88 |
| Aromatic 100 (mixture of aromatics and aliphatic petroleum distillate (available from Ohio Colombia Ashland Distributor)) | 16.29 |
| Aromatic 150 (mixture of aromatics and aliphatic petroleum distillate (available from Ohio Colombia Ashland Distributor)) | 2.89 |
| Hexanaphthene | 3.66 |
| Pimelinketone | 3.60 |
| Isobutyl isobutyrate | 1.00 |
| Thixotropic dispersion (in 80 weight % toluene, 20 weight % dimethylbenzene, 1 weight % methyl alcohol, 2 weight % ethanol, 0.12 weight % ethyl acetate, 2.5 weight % ethylbenzene, 02 %MIBK mixture, 4 weight % solid amide waxes) | 3.95 |
Embodiment 1-color: Arizona beige tackifier
| Component | Weight percent |
| The tackifier resins intermediate | 93.66 |
| Under stirring at low speed, add | |
| Aluminium pigment | 3.24 |
| Transparent iron oxide red dispersion (63.08%NVM:37.55 weight % tackiness agent and 25.33 weight % pigment) | 0.93 |
| Carbon black dispersion (35.80%NVM:30.74 weight % tackiness agent and 5.06 weight % pigment) | 1.71 |
| Titanium dioxide dispersion (61.56%NVM:41.41 weight % tackiness agent and 20.15 weight % pigment) | 0.46 |
The blue tackifier of embodiment 2-color: Arrival
| Component | Weight percent |
| The tackifier resins intermediate | 91.74 |
| Under stirring at low speed, add | |
| Carbon black dispersion (41.53%NVM:29.14 weight % acryloid cement and 12 weight % pigment) | 0.56 |
| Phthalocyanine blue dispersion (46.85%NVM:26.79 weight % resin glue and 20.06 weight % pigment) | 1.93 |
| Phthalocyanine blue dispersion (39.97%NVM:30.92 weight % acryloid cement and 9.06 weight % pigment) | 3.85 |
| Scribble the mica (100%NVM) of red oxide | 0.96 |
| Scribble the mica (100%NVM) of blue oxide | 0.96 |
| Aluminium pigment | 1.00 |
Embodiment 3-color: medium green pearly-lustre tackifier
| Component | Weight percent |
| The tackifier resins intermediate | 94.55 |
| Under stirring at low speed, add | |
| Carbon black dispersion (41.53%NVM:29.47 weight % tackiness agent and 12.04 weight % pigment) | 1.01 |
| Phthalocyanine green dispersion (50.18%NVM:25.12 weight % tackiness agent and 25.06 weight % pigment) | 1.73 |
| Glassy yellow oxide dispersion (63.00%NVM:35.70 weight % tackiness agent and 27.30 weight % pigment) | 1.23 |
| The green mica (100%NVM) of coating | 1.48 |
Embodiment 4-color: the red tackifier of Sport
| Component | Weight percent |
| The tackifier resins intermediate | 90.29 |
| Under stirring at low speed, add | |
| Carbon black dispersion (41.53%NVM:29.47 weight % tackiness agent and 12.06 weight % pigment) | 0.37 |
| The red dispersion of perylene (50.59%NVM:30.59 weight % tackiness agent and 20.00 weight % pigment) | 2.80 |
| Pinkish red dispersion (47.34%NVM:27.28 weight % tackiness agent and 20.06 weight % pigment) | 3.74 |
| Scribble the mica (100%NVM) of red oxide | 1.40 |
| Scribble the mica (100%NVM) of tawny oxide compound | 1.40 |
Pigment-binder wt in the table 2-prime coat is than (P/B
A) and undercoat in pigment-binder wt
Than (P/B
B)
| Embodiment-color | Total P/B A | Total P/B B | P/B A/P/B B |
| The 1-Arizona beige | 0.418 | 0.146 | 2.863 |
| 2-Arrival indigo plant | 0.398 | 0.253 | 1.573 |
| 3-medium green pearly-lustre | 0.267 | 0.119 | 2.244 |
| 4-Sport is red | 0.444 | 0.243 | 1.827 |
Table 3-test result
| (surface scribbles the tackifier of automobile undercoat color and varnish coating to coloured coating | Initial sticking power keeps % | The sticking power that (38 ℃) were placed after 96 hours under humidity keeps % | Δ E (under three viewing angles, comparing) with color standard | ||
| Embodiment-color | 25° | 45° | 75° | ||
| The 1-Arizona beige | 100 | 100 | 0.58 | 2.31 | 2.05 |
| 2-Arrival indigo plant | 100 | 100 | 1.19 | 0.70 | 1.38 |
| 3-medium green pearly-lustre | 100 | 100 | 1.48 | 0.37 | 0.21 |
| 4-Sport is red | 100 | 100 | .55 | .82 | 1.18 |
As shown in table 3, accurately mate and reproduce a series of color standards with multiple color.In addition, as the P/B in the table 2
A/ P/B
BShown in, even added the pigment of relative more amount in bonding agent composition, coating of the present invention still has fabulous sticking power to the TPO ground, even also is like this when light Arizona beige.
Claims (10)
1. two-layer or multiwalled coating, this coating comprises the ground that scribbles following coating: one or more layers colored primer layer, described colored primer layer is made by a kind of composition, and said composition contains one or more pigment and one or more are selected from the tackiness agent of resin or (being total to) polymkeric substance priming paint or tackifier; With
One or more layers undercoat color layer on described one or more layers colored primer layer, described undercoat color layer is made by a kind of composition, and described composition contains one or more pigment and one or more (being total to) polymkeric substance or resin;
It is characterized in that the color of described one or more layers undercoat color layer is identical with the color of described every one or more layers colored primer layer,
And, at weight ratio (total P/B) (P/B of the total pigment and the tackiness agent of the described composition that is used for making one or more layers described colored primer layer
A) be equal to or greater than weight ratio (total P/B) (P/B of the total pigment and the tackiness agent of the composition that is used for making one or more layers described undercoat color layer
B).
2. coating as claimed in claim 1 is characterized in that, also comprises varnish coating on described one or more layers undercoat color layer.
3. coating as claimed in claim 1 is characterized in that described ground comprises plastics or metal.
4. coating as claimed in claim 3 is characterized in that described ground is plastics, and comprises TPO (TPO).
5. coating as claimed in claim 1, it is characterized in that, described resin or (being total to) polymkeric substance priming paint or tackifier are selected from chlorinatedpolyolefins (CPO), modification isotactic polyprophlene (MPP), MPP multipolymer, MPP adducts, MPP multipolymer adducts, MPP alkyd resin mixture, MPP multipolymer alkyd resin mixture, chlorinatedpolyolefins alkyd resin mixture, chlorinatedpolyolefins acrylic polymers mixture, MPP acrylic polymers mixture, and their mixture.
6. two-layer or multiwalled coating, this coating comprises the ground that scribbles following coating: one or more layers tint lating, described colored primer layer is made by a kind of composition, said composition contains one or more pigment and one or more are selected from the tackiness agent of resin or (being total to) polymeric viscosifiers, and described tackifier are selected from chlorinatedpolyolefins (CPO), modification isotactic polyprophlene (MPP), the MPP multipolymer, the MPP adducts, MPP multipolymer adducts, the MPP alkyd resin mixture, MPP multipolymer alkyd resin mixture, the chlorinatedpolyolefins alkyd resin mixture, chlorinatedpolyolefins acrylic polymers mixture, MPP acrylic polymers mixture, weathering resistance chlorinatedpolyolefins adducts, weathering resistance MPP adducts and composition thereof; With
One or more layers undercoat color layer on described one or more layers colored primer layer, described undercoat color layer is made by a kind of composition, and said composition contains one or more pigment and one or more (being total to) polymkeric substance or resin;
It is characterized in that the color of described one or more layers undercoat color layer is identical with the color of described one or more layers colored primer layer.
7. coating as claimed in claim 6, it is characterized in that described tackifier are selected from the MPP alkyd resin mixture, MPP multipolymer alkyd resin mixture, the chlorinatedpolyolefins alkyd resin mixture, chlorinatedpolyolefins acrylic polymers mixture, MPP acrylic polymers mixture, weathering resistance chlorinatedpolyolefins and acrylic polymers adducts, weathering resistance chlorinatedpolyolefins and Synolac adducts, weathering resistance chlorinatedpolyolefins and carbamate adducts, weathering resistance chlorinatedpolyolefins and polyester adducts, weathering resistance MPP and acrylic polymers adducts, weathering resistance MPP and Synolac adducts, the MPP of weathering resistance and carbamate adducts, weathering resistance MPP and polyester adducts, and their mixture.
8. method of making coating, this method comprises:
One or more colored primers of coating or bonding agent composition on ground, thereby form the wet prime coat of one deck, described composition contains one or more pigment and one or more tackiness agents, and described tackiness agent is selected from resin or (being total to) polymkeric substance priming paint or tackifier;
Carry out drying, form the colored primer layer;
One or more layers pigmented basecoat composition of coating on the prime coat on the described ground, described composition contains one or more (being total to) polymkeric substance or resin glue and one or more pigment;
Be cured, form undercoat color layer and solidified coloured coating;
It is characterized in that the color of described undercoat color layer is identical with the color of described colored primer layer,
And, the total pigment in one or more described colored primers or bonding agent composition and the weight ratio of tackiness agent (total P/B) (P/B
A) be equal to or greater than weight ratio (total P/B) (P/B of total pigment in the described pigmented basecoat composition and tackiness agent
B).
9. method as claimed in claim 8, it also is included in before the described curing, and the wet pressing wetland is coated with one or more layers varnish coating composition on described one or more layers pigmented basecoat.
10. weather resistant coatings, it is made by the described method of claim 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60698004P | 2004-09-03 | 2004-09-03 | |
| US60/606,980 | 2004-09-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1743390A true CN1743390A (en) | 2006-03-08 |
| CN100383204C CN100383204C (en) | 2008-04-23 |
Family
ID=35997742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100990750A Expired - Fee Related CN100383204C (en) | 2004-09-03 | 2005-08-31 | Multilayer coatings having color matched adhesion promoters |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20060051513A1 (en) |
| CN (1) | CN100383204C (en) |
| CA (1) | CA2516969A1 (en) |
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| CN104114985A (en) * | 2011-09-30 | 2014-10-22 | 涂层国外知识产权有限公司 | Method for matching color and appearance of coatings containing effect pigments |
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| US3065102A (en) * | 1959-03-05 | 1962-11-20 | Du Pont | Process for inhibiting hydrogen popping |
| WO1985001694A1 (en) * | 1983-10-13 | 1985-04-25 | Ford Motor Company | Flexible coating compositions |
| US4615940A (en) * | 1985-05-20 | 1986-10-07 | Inmont Corporation | Primer produced opalescent coating |
| US4740566A (en) * | 1986-05-23 | 1988-04-26 | E. I. Du Pont De Nemours And Company | High gloss color keyed guide coat |
| US5322884A (en) * | 1991-06-18 | 1994-06-21 | Exxon Chemical Patents Inc. | Polyester-based coating compositions having high pigment-to-binder ratios |
| US5334652A (en) * | 1991-06-18 | 1994-08-02 | Exxon Chemical Patents, Inc. | Polyester-based coating compositions having high pigment-to-binder ratios |
| US5480939A (en) * | 1994-09-02 | 1996-01-02 | Bee Chemical Company | Primer for polyolefin containing chlorinated polyolefin and rubberized epoxy |
| US20030050388A1 (en) * | 2001-09-06 | 2003-03-13 | Strickland Debra S. | Aqueous coating composition |
| AU2003225640A1 (en) * | 2002-03-04 | 2003-09-22 | Valspar Sourcing, Inc. | High-reflectivity polyester coating |
| JP4324705B2 (en) * | 2002-12-10 | 2009-09-02 | 日本ビー・ケミカル株式会社 | How to paint resin parts |
| US20040176541A1 (en) * | 2003-02-21 | 2004-09-09 | Jackson Michael L. | Chlorine free and reduced chlorine content polymer and resin compositons for adhesion to plastics |
-
2005
- 2005-08-17 US US11/205,603 patent/US20060051513A1/en not_active Abandoned
- 2005-08-24 CA CA002516969A patent/CA2516969A1/en not_active Abandoned
- 2005-08-31 CN CNB2005100990750A patent/CN100383204C/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CN100383204C (en) | 2008-04-23 |
| US20060051513A1 (en) | 2006-03-09 |
| CA2516969A1 (en) | 2006-03-03 |
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